Sensitive layer on alpha suitable base and process of making same



Patented May 10, 1927.

UNITED STATES PATENT OFFICE.

MAXIMILIAN PAUL SCHMIDT AND WILI-IELM KRIEGER, OF BIEBRIOH-ON-THE-RHINE,

GERMANY, ASSIGNORS TO KALLE & 60., AKTIENG-ESELLSCHAFT, OF BIEBRICH-ON-THE-RHINE, GERMANY, A CORPORATION OF GERMANY.

SENSITIVE LAYER ON A SUITABLE BASE AND PROCESS OF MAKING SAME.

No Drawing. Application filed .Tune 19, 1925, Serial No. 38,288, and inGermany May 28, 1924.

In U. S. Patent No. 1,444,469 of Gustav Kogel, filed September 12, 1922,a process is described for the production of layers sensitive to lightand of great technical value,

particularly for making light copy paper, by means of the so-calleddiazo-anhydrides. By the application of these layers it is possible toobtain directly positive pictures from positives.

In U. S. Patent No. 1,444,469 it is set out that diazo compounds can beapplied on the base simultaneously with the azo-dyestuff components,without impairing there by the effect of the picture to be produced.

Further it has been shown that the coupling of the diazoandazo-components can be effected by means of a gaseous alkali, forinstance ammonia, which permits the development of the picture withouthaving to 20 use any liquid.

It has been proposed to use an acid for preventing a premature couplingof the components during their storage. Thus it is possible to applydiazo compounds of dili'er- '25 ent kind together with azo components.If

diazo compounds other than diazo-anhydrides are chosen, it is necessaryto add thereto .a considerable quantity of an acid, for instancesulphuric acid, in order to prevent a premature coupling of thecomponents, but this addition impairs considerably the durability of thepaper-fibre. Moreover the simplediazo compounds involve the disadvantagethat they .are scarcely colored so that it is very difficult -to seewhen the bleaching is finished.

Now we have found that there can be obtained papers which are equallydurable or nearly as durable and capable of being stored as thosedescribed in U. S. Patent No. 1,444,-

469 without having to add a considerable quantity of an acid, b using asdiazo components compounds W ich may be regarded as diazo anhydrides ina broad sense and which may be presumed to have been produced fromdiazonium compounds with elimination of water. We prefer to use diazocompounds formed from amino compounds containing at least one otheramino group substituted or not.

These diazo compounds possess, like the diazo anhydrides alreadymentioned, the

necessary stability and they are also more or less colored.

As such diazo components there may be used amino-diazo compounds, forinstance the diazo con'ipounds 'lrom p-diamiues andderi-vatives thereofand also aminodiphe nylamines such, for instance asphenyliminoquinonediazide (comp. Hantzsch & Reddelin, DieDiazoverbindungen Berlin 1921, page ft), dialkylamino-oaniline and itssulphonic acid.

For our new process there may also be used the diazo compounds obtainedfrom aminocarbazoles, being also amino compounds, in which one of theamino groups is substituted by carbon atoms standing in a closednucleus, aminofiuorene, aminodiphenylcueoxide and similar stable diazobodies, which arealso colored and behave in a like manner.

As described in the above mentioned U. Patent No. 1,444,469 metallicsalts may simultaneously be added to the layer sensitive to light, andthe new process may be carried out according to any of the variousmethods described in the previous patent. 1ustead of incorporating themetallic salts into the light-sensitive layer there may also be used themetal compounds of the diazoor azo-components in question or of bothcomponents in case they contain salt-forming groups or, when combinedwith metal salts, form double salts. In this case it is advantageous todevelop the picture after exposure to light by means of a gaseousalkali, which latter may be produced according to any known method Thedevelopment of the picture may however also be effected in an aqueousalkaline bath and then the metal salts added to the alkali bath.

The other amino groups of the amino compounds, from which the diazocompounds are formed, can be substituted or not.

The diazo anhydrides already claimed in U. S. Patent No. 1,444,469 areexcluded from what we claim in our present application.

The following examples illustrate our invention:

1. 13.6 parts by weight of o-aminodimethylaniline are diazotized in theusual manner and in this diazo solution, which has a deep yellow color,8 parts of resorcylic acid and parts of nickel sulfate are dissolved.The solution is made up to one liter and used for being spread on thedesired base (paper).

The layers obtained after drying yield, when exposed to light andtreated with an alkali, brownish-orange copies.

2. 10 parts by weight of phenyliminoquinonediazidesulfate, 9 parts byweight ot resorcylic acid and parts by weight oi nickel sulfate (NiSQtFH O) are dissolved in 1000 parts by volume of water and the base ispainted over with this solution.

The layers so obtained are exposed to light in the usual manner and bythen treat ing them with an alkaline agent, such as gaseous ammonia orsodium carbonate, 1mmediate brown positive copies are produced.

3. 10 parts by weight of 1')-iminoquinonediazidesulfonic acid, which isobtained by diazotizing p-phenylenediaminesulfonic acid, are dissolvedin 1000 parts by volume of water together with 20 parts of l-amino-S-oxynaphthalene-3.6-disulfonic acid (H- acid) and the base is paintedover with this solution.

The layers so obtained after being exposed to light and subsequentlydeveloped with an alkaline agent, for instance gaseous ammonia, yielddark bluish-violet positive copies.

4t. 12 parts by weight of dimethyliminoquinoned.iazidesulfonic acid,which may be obtained by diazotizing p-dimethylaminoaniline sultonicacid, and 20 parts by weight of fi-naphthol-3.6-disulfonic acid are Idissolved in 1000 parts by volume of water and the base is painted overwith this solution.

In the same way as described in Example 2, brown positive copies areobtained.

10 parts by weight of phenyliminoquinonediazidesultate, obtained bydiazotizing -aminodiphenylamine, are dissolved in .1000 parts by volumeof water together with 20 parts by weight of ,8-naphthol-3.6- disultonicacid and applied upon a suitable base for instance paper. The layers soobtained when treated as indicated in EX- amples 3 and l yield darkviolet positive copies.-

(5. 9 parts by weight of 3-aminocarbazole are diazotized in the usualmanner and in this diazo solution are dissolved: 8 parts by weight ofresorcylic acid and 15 parts of nickel sulfate. The resulting solutionis made up to one liter and spread on a base. The layers so obtained,after being dried, exposed to light under a positive or negative anddeveloped with an alkali, yield brown copies.

lVe do not claim any diazo compounds described and claimed in U. S.patent of liogel No. 1,44%, l09, tiled Sept. 12, 192

\Ve claim:

1. Process for producing sensitive layers on a suitable base, consistingin covering the base with a diazo compound being formed from aminocompounds containing at least one other amino group and an azo dyestuttcomponent.

2. Process for producing sensitive layers on a suitable base, consistingin covering the base with a diazo compound being formed from aminocompounds containing at least one other amino group. an azo-dyestutl'component and a metal salt.

3. Process For producing sensitive layers on a suitable base, consistingin covering the base with a diazo compound being formed from aminocompounds containing at least one other amino group substituted or not,an alkali and a metal salt.

4-. As new products, sensitive layers on a suitable base, consisting ofdiazo compounds being formed from amino compounds containing at leastone other amino group, and an aZo-dyestuti con'iponent.

5. As new products, sensitive layers on a suitable base, consisting ofdiazo compounds being formed "from amino compounds ('ol". taining atleast one other amino group, and a metal salt.

6. As new products, sensitive layers on a suitable base, consisting ofdiazo compounds being formed "from amino con'ipounds containing at leastone other amino group, and an alkali.

7. As new products, sensitive layers on a suitable base, consisting ofdiazo compounds being formed from amino compounds containing at leastone other amino group, an axe dyestutt' component: and a metal salt.

8. As new products, sensitive layers on a suitable base, consisting of(liazo compounds being formed from amino compounds con taining at leastone other amino group, an alkali and a metal salt.

In testimony whereof we hereunto allix our signatures.

Dr. MAXIMILIAN PAUL SCHMIDT. Dr. WlLllELll'l KRIEGER.

DISCLAIMER 1,628,279.Ma:m'milian Paul Schmidt and Wilhelm Krieger,Biebrich-on-the-Rhine, Germany. SENSITIVE LAYER ON A SUITABLE BASE ANDPROCESS OF MAKING SAME. Patent dated May 10, 1927. Disclaimer filedFebruary 3, 1940, by the assignee, Kalle ct C0. Alctiengesellschajt.

Hereby disclaims claims 3, 5, 6, and 8 of said Letters Patent,

The comma and Words aminofiuorene, aminodiphenyleneoxide, appearing onpage 1, lines 69 and 70 of said Letters Patent, and

From the scope of claims 1, 2, 4, and 7 of said Letters Patent, thosediazo compounds being formed from amino compounds containing at leastone other amino group which compounds may not be regarded as diazoanliydrides in a broad sense and which compounds may not be presumed tohave been produced from diazonium compounds with elimination of water.

[Ojfict'al Gazette February 27, 1940.]

